Detergent compositions



United States Patent Office 3,341,459 Patented Sept. 12, 1967 3,341,459DETERGENT COMPOSITIONS Jerry Edison Davis, Cincinnati, Ohio, assignor toThe Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio NDrawing. Filed May 25, 1964, Ser. No. 370,036 Claims. (Cl. 252--137)This invention relates to detergent compositions especially effective incool water. The term cool water as used in describing this invention isintended to mean aqueous washing solutions having a temperature within arange of from about 40 F. to about 100 F This temperaturecharacterization more generally is intended to mean temperaturessubstantially below those which are commonly associated with the usualhousehold parlance of hot water.

Some garments or fabrics cannot be washed in hot water, i.e., say inexcess of about 110 F., without running the risk of damaging thematerial by shrinkage or altering the handle or feel of the fabric. Forsuch laundering situations fabric and material manufacturers recommendthe use of cool water. Conventional detergents, however, are known to beless effective as cleaning agents, i.e., removing soil, in cool aqueoussolutions. There is no question that the presently available detergentcompositions can be used under such circumstances but with varyingdegrees of successful cleaning results. To compensate for the poorercleaning performance, consumers are generally inclined to use excessiveamounts of the detergent compositions. Such economic waste isunfortunate but has been necessary prior to the present invention due tothe lack of detergent compositions which are specially formulated to beeffective cleaning agents in cool water.

It is a primary object of this invention to provide a detergentcomposition which is especially effective in cleaning soiled fabrics incool aqueous washing solutions. Another object of the present inventionis to provide novel built detergent compositions consisting essentiallyof an alkyl polyethoxy amine oxide detergent compound having the generalformula:

. R wherein R is an alkyl radical containing from about to about 18carbon atoms. R and R are each methyl, ethyl or ethanol, and n averagesfrom 2 to 10; and a builder material selected from the group consistingof water soluble inorganic alkaline builder salts, organic alkalinesequestrant builder salts and mixtures thereof, the ratio of weight ofthe detergent to the builder in the range of from about 4:1 to 1:20.Other objects will be readily apparent to those skilled in the .art froma review of the following detailed description of the present invention.

It has now been surprisingly discovered that certain alkyl polyethoxyamine oxide compounds having the formula set forth above possessunusually effective cleaning .power in aqueous solutions having the cooltemperatures defined above. These unexpected cleaning properties of thecompounds of this invention are demonstrated by the experimental datapresented below. Of the alkyl polyethoxy amine oxides described herein,best cool water cleaning results are obtained when R is dodecyl ortetradecyl, R and R are each methyl and n averages about 3.

The alkyl polyethoxy amine oxide compounds to which the presentinvention pertains can be prepared according to any convenient process.The alkyl can be derived from synthetic sources such as syntheticdodecanol or from natural sources such as coconut oil or tal'low fromwhich fatty alcohols are made. Such processes are illustratedhereinafter but other methods can be used.

Alkyl polyethoxy amine oxide compounds can be prepared by oxidizing,with a strong oxidizing agent such as hydrogen peroxide, thecorresponding alkyl polyethoxy amine. This .amine in turn can beprepared by reacting a polyethoxylated alcohol or a polyethoxylatedalcohol sulfate with an appropriate secondary amine such asdimethylamine, diethylamine, or diethanolamine. Preferably, aneutralized, sulfate polyethoxylated alcohol is used in the reactionwith the secondary amine. Polyethoxylated alcohols are known and can beformed either by reacting fatty alcohol with 2 to 10 moles of ethyleneoxide or by reacting alkyl bromides with sodium glycolate in excessdiethylene glycol or triethylene glycol. The former reaction results notin a uniform product, but a mixture of alcohol ethers containing varyingmolar amounts of ethylene oxide wherein the average molar amount ofethylene oxide per ether corresponds to the moles of ethylene oxidereacted with the alcohol. In the latter reaction a uniform product doesresult; for example, if diethylene glycol is used, the reaction productis substantially all diethoxylated alcohol. As used herein, the termalkyl polyethoxy amine oxide includes a single compound containingpolyethoxy ether linkages or a mixture of such compounds where theaverage molar proportion of ethylene oxide is noted.

A preferred alkyl polyethoxy amine oxide was prepared as follows: 2.9pounds of the sodium salt of the sulfated reaction product of coconutfatty alcohols and three moles of ethylene oxide was reacted in 6 poundsof water with dimethylamine, in a molar proportion of dimethylamine tothe sulfated reaction product of 10:1, in an autoclave at 350 F. and 425p.s.i. pressure for two hours. The coconut fatty alcohol comprised about2% decanol, 66% dodecanol, 23% tetradecanol and 9% hexadecanol. Theresulting reaction mixture separated into two phases. The aqueous upperphase contained the alkyl polyethoxy amine in a yield about 96.5% oftheoretical; the upper phase was separated and water was removed from itwith vacuum. Fifty grams of the resulting dimethyl coconut alkylpolyethoxy amine was oxidized to the amine oxide with 220 grams of 30%aqueous hydrogen peroxide.

While the class of alkyl polyethoxy amine oxide compounds just describedcan be employed alone as cool water detergent compounds on easilycleanablematerials, more outstanding performances are obtained when theyare mixed with other ingredients which enhance or build the cleaningpowder of detergent compounds, i.e., socalled builder or boostercompounds. Such built or heavyduty detergency is essential withhard-to-clean fabrics such as cotton. According to the presentinvention, therefore, the alkyl polyethoxy amine oxide detergentcompounds are preferably used in conjunction with such other ingredientswhich substantially improve cleaning power. While the term builder isused herein. in its singular form, the term is intended to covermixtures of such compounds also. i

The present invention pertains to detergent compositions consistingessentially of a water soluble inorganic alkaline builder salt or awater soluble organic alkaline sequestrant builder salt, or mixturesthereof, and a member of the class of alkyl polyethoxy amine oxidedetergent compounds having the general formula described above, whichcomposition consists essentially of the detergent compounds and abuilder material in a ratio by weight of detergent to builder of about4:1 to about 1:20. The preferred ratio of the detergent to builder is1:1 to about 1:10. The ratios and percentages referred to herein are allby weight unless otherwise noted.

The built detergent compositions of this invention can be prepared asgranular, tablet, or liquid compositions and perform effectively. Withinthe above detergent to builder ratio range, granular and tabletcompositions offering outstanding cool water washing performance cancontain from 4% to 50% by weight of the alkyl polyethoxy amine oxidedetergent compound, the balance comprising essentially a selectedbuilder material or mixtures of builders and any optional ingredientsemployed. Preferred granular and tablet compositions contain from about15% to about 35% by weight of the alkyl polyethoxy amine oxide detergentwith the balance comprising the essential builder materials and otheringredients. On the other hand, built liquid detergents preparedaccording to the present invention have a slightly modified compositionto compensate for the requirement of a liquid vehicle. Such liquidcompositions can contain from about 2% to 25% by weight of the alkylpolyethoxy amine oxide detergent, preferably from about 8% to about 18%,with the remainder comprised essentially of builder ingredients, and, ofcourse, a liquid vehicle as described below. The ratio set forth abovebetween the detergent and builder applies equally to all physical formsof the composition.

Water soluble inorganic alkaline builder salts which can be used in thisinvention alone or in admixture are alkali metal carbonates, borates,phosphates, polyphosphates, bicarbonates and silicates. Ammonium orsubstituted ammonium, e.g., triethanol ammonium, salts of thesematerials can also be used. Specific examples of suitable salts aresodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodiumand potassium pyrophosphate, sodium and ammonium bicarbonate, potassiumtripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate,sodium orthophosphate and potassium bicarbonate. The preferred inorganicalkaline builders according to this invention are alkali metaltripolyphosphates for built granular and tablet compositions and alkalimetal pyrophosphates for built liquid compositions. Potassium is thepreferred alkali metal used in liquid compositions and sodium finds bestapplication for granular or tablet compositions.

Examples of suitable organic alkaline sequestrant builder salts used inthis invention alone or in admixture are alkali metal, ammonium orsubstituted ammonium, aminocarboxylates, e.g., sodium and potassiumethylenediaminetetraacetate, sodium and potassiumN-(2-hydroxyethyl)-ethylenediaminetriacetates, sodium and potassiumnitrilotriacetates and sodium, potassium and triethanolammonium N (2-hydroxyethyl)-nitrilodiacetates. Mixed salts of these polycarboxylatesare also suitable. The alkali metal salts of phytic acid, e.g., sodiumphytate are also suitable as organic alkaline sequestrant builder salts(see US. Patent 2,739,942). Ethane-l-hydroxy, l-diphosphonate asdescribed in copending patent application Ser. No. 187,327, filed Apr.15, 1962, can also be used as a builder, either alone or in mixtureswith other builder compounds. Other suitable builders include methyleneand ethylene diphosphonates and their derivatives.

Besides the builders being used in the form of mixtures it is alsopossible according to the present invention to use the alkyl polyethoxyamine oxide compounds of this invention in combination with othercleaning agents such as anionic, nonionic and zwitterionic organicdetergent surfactant compounds. When it is desired to use the alkylpolyethoxy amine oxide compounds in combination with other detergentcompounds, the ratio of the amine oxide to such other detergent compoundis about 10:1 to 1:5. If for any reason, it is desired to use an alkylpolyethoxy amine oxide in admixture with another detergent compound asthe active portion of a cleaning composition, the ratio of such amixture to the builder salt should be within the previously prescribedrange of 4:1 to 1:20. A composition prepared along these lines cancontain from 4% to 50% of such a mixture and 5% to 85% of a builder saltselected from water soluble inorganic alkaline builder salts, watersoluble organic sequestrant builder salts, and mixtures thereof, andobserving this ratio range.

Examples of anionic soap detergents which can be used in admixture withthe alkyl polyethoxy amine oxide, if desired, are the sodium, potassium,ammonium and alkylolammonium salts of higher detergent range fatty acids(C -C Particularly useful are the sodium and potassium salts of themixtures of fatty acids derived from coconut oil and tallow, i.e.,sodium or potassium tallow and coconut soap. Examples of suitableanionic organic nonsoap detergents are: alkylglycerylethersulfonates;alkyl sulfates; alkyl monoglyceride sulfates or sulfonates;alkylpolyethenoxy ether sulfates; acylsarcosinates; acyl esters ofisethionates; N-acyl-N-methyl taurides, alkylbenzenesulfonates whereinthe alkyl substituent is straight chain or branched chain; sulfonated aolefins alkylphenol polyethenoxy sulfonates. In these compounds thealkyl and acyl groups, respectively, contain 10 to 20 carbon atoms. Theyare used in the form of water soluble salts, the sodium, potassium,ammonium, and alkylolammonium salts, for example. Specific example are:sodium lauryl sulfate, potassium N-methyl-N-lauroyl tauride;triethanolammonium dodecylbenzene sulfonate.

Examples of nonionic organic detergents which can be used in thecompositions of this invention, if desired, are: polyethylene oxidecondensates of alkylphenols wherein the alkyl group contains from 8 to15 carbon atoms (e.g., t-octylphenol) and the ethylene oxide is presentin a molar ratio of ethylene oxide to alkylphenol in the range of 8:1 to20:1; condensation products of ethylene oxide with the product resultingfrom the reaction of propylene oxide and ethylene diamine wherein themolecular weight of the condensation products ranges from 5000 to11,000; the condensation products of from about 5 to 30 moles ofethylene oxide with one mole of a straight or branched chain aliphaticalcohol containing from 8 to 18 carbon atoms, e.g., lauryl alcohol;higher alkyl dilower alkyl amine or phosphine oxides, e.g.,dodecyldimethylamine oxide or dodecyldimethyl phosphine oxide; alkylmethyl sulfoxides such as dodecyl methyl sulfoxide.

Zwitterionic synthetic detergent surfactant compounds which can be usedare broadly described as derivatives of aliphatic quaternary ammoniumcompounds, in which the aliphatic radical can be straight chain orbranched and wherein one of the aliphatic substituents contains fromabout 8 to about 18 carbon atoms and one contains an anionic watersolubilization group, e.g., carboxy, sulfo, or sulfato. Examples ofcompounds falling within this definition are: 3(N,N-dimethyl-N-hexadecylammonia)- 2-hydroxypropane-l-sulfonate and thecorresponding dodecyl and tetradecyl homologs and 3-(N,N-dimethyl-N-dodecylammonio) propane l-sulfonate and the corresponding hexadecyl andtetradecyl homologs.

The discovery that the compositions containing members of the class ofcompounds described in this invention show exceptional cool waterdetergency was unpredictable in view of the fact that there is, as yet,virtually no generally accepted theory or background information on themechanics of cool water detergency. Moreover, cleaning agents such assodium tallow alcohol sulfate or sodium dodecylbenzenesulfonate, forexample, which are good hot water (-140 F.) detergent compounds exhibita minimum of cleaning activity in cool water. One would be led to assumethat the alkyl polyethoxy amine oxide compounds of the present inventionshould be, comparatively speaking, as poor as any other conventionaldetergent compounds when used in cool water; certainly there is noreason to expect that they would behave otherwise. As has beendiscovered, however, the compositions containing the alkyl polyethoxyamine oxide compounds of this invention are substantially more effectivein cool water than some of the commonly used commercially availabledetergent compositions are in hot water. It can, therefore, be seen thatthe structure of a given detergent compound which is effective in hotwater has little or no discernible relation to the effectiveness of suchcompounds in cool water.

It has also been found that maximum cleaning occurs with thecompositions of this invention when the pH of the washing solution, atcool water temperatures as herein defined is within the range of fromabout 8 to about 12 with the preferred pH range being 9.5 to 11.5. Usingnormal amounts of water for washing, the desired pH of the solution canbe obtained by incorporating into the compositions of this invention anormal amount of a strongly alkaline material such as sodium silicate,i.e., up to about 10% by weight. The silicate acts as a buifer and alsoas a corrosion inhibitor.

A laundering method incorporating the discovery of the present inventioncan be practiced in a number of different ways. Preferably the washingstep is followed by rinsing and drying the fabrics. The washing solutioncan be prepared by adding the granular, tablet or liquid detergentcomposition prepared according to this invention to any container whichcontains cool water at a temperature ranging from about 40 F. to about100 F., usually about 80 F. The detergent composition concentration insolution can range from about to .50% by total weight, and should beadded in sufficient amount to provide a concentration of at least 0.005%of the alkyl polyethoxy amine oxide detergent compound. The fabrics canbe added to the container or washer before or after the washing solutionis added. As is usual in a washing step, the fabrics are then agitatedin the detergent solution. While the period of time may vary, anautomatic agitator type washer, generally employs a washing cycle whichranges from 8 to 15 minutes.

After the washing step, the washing liquor is drained off or the fabricsare separated from the liquor and thereafter the fabrics are rinsed inclean water. The fabrics can be rinsed as many times as desired in orderto insure that washing liquor is removed. Using an automatic washer, ithas been found that about four spray rinses and one deep rinse areusually sufficient for this purpose. Between and after rinsing steps,the bulk of the rinse water .is usually drawn from, or spun out of thefabrics. After rinsing, the fabrics are dried. Although rinsing anddrying are usual and desirable steps, the important advantage of theinvention is achieved in the washing step.

The surprisingly efiective cool water performance characteristics of thealkyl polyethoxy amine oxide compounds described herein are demonstratedby conducting the following tests.

Naturally soiled fabric swatches (desized cotton print cloth) werewashed for ten minutes in an aqueous solution of a detergent compositionhaving a pH of and containing 7 grains equivalent CaCO per gallonhardness. Detergent compositions were prepared containing only basicessentials, i.e., a detergent compound and a builder compound. Thedetergent compounds were respectively (1) a representativealkylpolyethoxy amine oxide, i.e., the coconut alkyl dimethyl polyethoxyamine oxide containing an average of 3 moles of ethylene oxide describedabove; and (2) sodium tetrapropylenebenzene sulfonate (ABS); the buildercompound in each composition was sodium tripolyphosphate. By using thesame builder compound in each composition, any variations in cleaningperformance could be directly attributed to the specific detergent beingevaluated. The concentration by weight in the washing solution of thedetergent compound was 03%; the concentration of the builder was .06%.

These two compositions were compared for their soil removal properties,the alkyl polyethoxy amine oxide in a washing solution at 80 F. and theABS in a washing solution at 140 F. Soil removal, expressed as apercentage of the soil originally present on the soiled swatches, was70% for the alkyl polyethoxy amine oxide and 64% for the ABS. Theamounts of soil present (a) on the cloth swatches after washing anddrying and (b) on similar unwashed swatches were determined by solventextraction.

The alkyl polyethoxy amine oxide detergent compound gave results inwater at F. which were superior to the results obtained with a formulawherein sodium tetrapropylenebenzenesulfonate (ABS) was used as acleaning agent in a washing solution having a temperature of 140 F.Sodium tetrapropylenebenzenesulfonate is widely regarded as a standardfor comparison. Compositions which perform better than ABS at 140 F.generally can find application and commercial acceptance as detergentformulations. In situations such as the present invention where superiorcleaning is obtained with different compounds at low temperatures, i.e.,80 F.. the results are even more remarkable.

The same superiority of the alkyl polyethoxy amine oxide compound at 80F. over ABS at 140 F. was demonstrated in a similar washing testemploying soiled mens white dress shirts where the collars and cuffswere used as the basis for comparing cleaning ability of compositionsemploying these two detergent compounds. The superior cleaning abilityof the alkyl polyethoxy amine oxide was particularly manifested in thewhiteness of the collars and cuffs.

Substantially the same performance advantages are observed by thehousewife when doing the home laundry in water ranging from 40 to 100 F.Woolens and syn thetic fibers washed in the same manner are cleaned aseificiently when washed according to the process of this invention andusing the compositions of this invention as they would be if they werewashed in conventional detergent compositions at hot water temperatures,yet a minimum of shrinkage and wrinkling takes place and the feel of thewool is preserved to a greater extent.

While the compositions of this invention are outstandingly eifective inwater at a temperature ranging from 40 F. to 100 F. the preferredtemperature range is about 60 F. to F. Below about 60 F. it has beenfound that the granular detergent compositions of this invention aresomewhat slower to dissolve, consequently it is preferred to use liquidcompositions at such lower temperatures.

The following composition-s further illustrate the manner in which theinvention can be practiced; they provide improved cool Water detergencycharacteristics similar to that demonstrated in the soil removalcomparison set forth above. The pHs of the compositions in aqueoussolutions ranged from 9.5 to 11.5 at concentrations of about 0.25%.Included are both liquid and granular formulations. The examples are notto be construed as limiting the scope of the invention claimedhereinafter. These compositions are useful in automatic washers andconventional type washers employing cool water, 40 F. to F., as well ashand washing operations.

EXAMPLE I Solidgranules Percent Dimethyl dodecyl polyethoxy amine oxidecontaining an average of three moles of ethylene oxide 17.5

Sodium tripolyphosphate 50.0

Sodium silicate (Na O:SiO =1:2.5) 10.0

Sodium sulfate 17.5

Moisture 5.0 EXAMPLE II Compressed granules-tablet Diethyl tetradecylpolyethoxy a-mine oxide containing an average of five moles of ethyleneoxide 31 Sodium tripolyphosphate 52 Trisodium phosphate 10 Moisture 7 7EXAMPLE 1v Solid-granul s oxide 25 Sodium tripolyphosphate 35 Sodiumcarbonate 10 Sodium silicate (Na O:SiO =1:2.5) 5 Moisture 5 EXAMPLE VSalim-granules Dimethyl decyl polyethoxy amine oxide containing anaverage of two moles of ethylene oxide Diethanol tetradecyl polyethoxyamine oxide containing an average of four moles of ethylene oxide 10Sodium tallow alcohol sulfate 10 Ethane-l-hydroxy-l,l-diphosphonate 20Sodium tripolyphosphate 10 Sodium nitrilotriacetate 10 Sodium sulfate 8Sodium silicate (Na O:SiO =1:2.5) 11 Moisture 11 EXAMPLE VI Liquid3-(N,N dimethyl-N-dodecyl ammonio)-2-hydroxy propanel-sulfona-teDimethyl dodecyl polyethoxy amine oxide containing three moles ofethylene oxide 10.0 Tetrapotassium pyrophosphate 19.0 Sodium silicate(Na O:SiO =1:1.6) 3.8 Potassium toluene sulfonate 8.5 Carboxymethylhydroxyethyl cellulose .3 Water Balance EXAMPLE VII Liquid Dimethyldodecyl polyethoxy amine oxide containtainin-g two moles of ethyleneoxide 6.0 Sodium dodecyl benzene sulfonate 6.0

Tetrapotassium pyrophosphate 20.0

Sodium silicate (Na O:SiO =1:1.6 3.8 Potassium toluene sulfonate 8.5Carboxymethyl hydroxymethyl cellulose .3 Water Balance EXAMPLE VIIISolid-granules Dimethyl tetradecyl polyethoxy amine oxide containthreemoles of ethylene oxide 15 Condensation production of 10 moles ofethylene oxide and one mole of tallow fatty alcohol 5 Dodecyl methylsulfoxide 5 Percent Coconut oil soap 5 Sodium tripolyphosphate 50 Sodiumethylene diamine tetraacetate 20 It will be appreciated that the alkylpolyethoxy amine oxide compounds used in the present invention can beincorporated into many other liquid or granular detergent compositionswith suitable adjustments being made in the other components.

Materials which are considered normal and desirable additives in liquidor granule detergent compositions can be added to the compositions ofthis invention without adversely affecting or modifying basic cleaningcharacteristics. For example, a tarnish inhibitor such as benzotriazoleor ethylene thiourea may be added in amounts up to about 1%.Fluorescers, perfume, bleaching agents, color, antiredeposition agents,antibacterial agents, thickening agents, opacifiers, and blending orviscosity control agents, while not essential in the compositions ofthis invention, may also be added.

While the present invention finds exceptional application in cool waterwashing situations, the compositions described herein can also be usedin conjunction with warm and hot water.

What is claimed herein is:

1. A detergent composition consisting essentially of an amine oxide inthe following general formula wherein R is an alkyl radical containingfrom 12 to 14 carbon atoms, R and R are each methyl, and n averages 3,and sodium tripolyphosphate, the ratio by weight of said amine oxide tosaid tripolyphosphate being in the range of about 4:1 to about 1:20.

2. The detergent composition of claim 1 wherein the ratio of saiddetergent compound to said builder is from 1:1 to about 1:10, by weight.

3. The detergent composition of claim 1 in which the aqueous solutionhas a pH of from about 8,to about 12.

4. The detergent composition of claim 3 wherein the preferred pH rangeis between 9.5 and 11.5.

5. A laundering process comprising the steps of immersing soiled fabricsand garments into an aqueous solution having a temperature within therange of from F. to F., and a pH of from about 8 to about 12, saidaqueous solution containing from about 05% to 50% by total weight of thedetergent composition of claim 1.

References Cited UNITED STATES PATENTS 3,202,714 8/1965 Zimmerer et al.252137 X 3,206,512 9/1965 Koebner et al 252-152 X 3,235,506 2/1966 Diehlet al. 252-152 X LEON D. ROSDOL, Primary Examiner.

S. E. DARDEN, Assistant Examiner,

1. A DETERGENT COMPOSITION ESSENTIALLY OF AN AMINE OXIDE IN THEFOLLOWING GENERAL FORMULA
 5. A LAUNDERING PROCESS COMPRISING THE STEPSOF IMMERSING SOILED FABRICS AND GARMENTS INTO AN AQUEOUS SOLUTION HAVINGA TEMPERATURE WITHIN THE RANGE OF FROM 60* F. TO 90*F., AND A PH OF FROMABOUT 8 TO ABOUT 12, SAID AQUEOUS SOLUTION CONTAINING FROM ABOUT .05% TO.50% BY TOTAL WEIGHT OF THE DETERGENT COMPOSITION OF CLAIM 1.